WO2006035708A1

WO2006035708A1 - Coating composition for protecting pattern layer for hydraulic transfer, decorated formed article and method for production thereof

Info

Publication number: WO2006035708A1
Application number: PCT/JP2005/017623
Authority: WO
Inventors: Hiroyuki Suzuki; Tatsuya Yano; Takahiro Kodama
Original assignee: Origin Electric Company, Limited; Trinity Industrial Corporation
Priority date: 2004-09-28
Filing date: 2005-09-26
Publication date: 2006-04-06
Also published as: JPWO2006035708A1; JP4510831B2; CN101018677B; CN101018677A; TW200621916A

Abstract

A coating composition for protecting a pattern layer for hydraulic transfer which uses, onto a transfer formed product obtained by the hydraulic transfer of a pattern layer having been formed through printing or application on a film base material being soluble in or swelling with water onto a polypropylene based resin formed article, a protective coating having adhesiveness to both of said polypropylene based resin formed article and said pattern layer, wherein use is made of a protective coating film obtained by curing a hydroxyl group containing resin composition (P) prepared by subjecting a resin component (A) comprising a chlorinated polypropylene based resin and a poly-ol component (B) comprising an acryl polyol selected among cyclohexyl methacrylate, t-butyl methacrylate, styrene and hydroxyethyl methacrylate to a graft polymerization, with a polyisocyanate based curing agent (Q).

Description

Specification

Coating composition for protection of hydraulic transfer pattern layer, decorative molded product and production method thereof

[0001] The present invention relates to a transfer molded product obtained by hydraulically transferring a pattern layer formed by printing or coating on a water-soluble or swellable film base material onto a polypropylene-based resin molded product. The present invention relates to a coating composition that produces a protective coating film having excellent adhesion to both the polypropylene-based resin molded product and the patterned layer, a decorative molded product protected by the coating composition, and a method for producing the same.

This application claims priority based on Japanese Patent Application No. 2004-282562 filed with the Japan Patent Office on September 28, 2004, the contents of which are incorporated herein by reference.

Background art

Recently, a hydraulic transfer method has been used to decorate various types of patterns such as wood grain and lattice patterns on a resin molded product having a complicated surface shape. This method uses a water-insoluble or water-swellable film with a water-insoluble component and a transfer film on which a predetermined pattern layer (also referred to as a transfer layer) is printed on the water surface in the transfer tank. This is a method in which a pattern layer is transferred onto the surface of a resin molded product by floating and placing the resin molded product on it and submerging it in water.

As the resin molded products, resin molded products such as ABS resin, acrylic resin, and polycarbonate resin have been used, but the adhesive strength of the transferred pattern layer to the resin molded product is not sufficient. It was insufficient to provide chemical resistance such as heat resistance and alkali resistance, as well as durability such as heat resistance, weather resistance, and abrasion resistance. Therefore, a protective coating film is applied on the pattern layer for the purpose of protection. With this protective coating, it is possible to impart a sense of transparency and a fleshiness to the patterned layer just by satisfying the various performances mentioned above, and to have further design.

[0003] However, in recent years, polypropylene-based resin molded products are widely used for interior and exterior parts of automobiles in terms of recyclability and cost. Conventional protective coatings are acrylic or urethane based on adhesion to ABS resin, acrylic resin, polycarbonate resin, etc. Paints have been used, but it is not sufficient to adhere to polypropylene-based resin having extremely low polarity and difficult adhesion, and its adhesive strength decreases with time or due to heat, light, humidity, etc. There was a problem.

[0004] In Japanese Patent Laid-Open No. 2001-232998, a transfer film having a printing pattern activated by an activator is floated on a liquid surface, and a transfer target is placed below the liquid surface relative to the transfer film. In the hydraulic transfer method, in which the printing pattern on the transfer film is transferred by hydraulic pressure, and a protective coating film is formed on the transfer target to which the printing pattern has been transferred, the printing pattern is activated. The activating agent contains a binder resin formed by adding a lyophilic component to chlorinated polyolefin, and the protective coating comprises the transfer material, the printed pattern thereon and the protective coating. And a method of forming it on the transferred material via an intermediate coating film having adhesiveness to both (see Patent Document 1).

However, with this technology, the transfer film is activated with an activator containing a binder resin and then transferred to a Tg of 50 ° C or higher on the transferred material onto which the print pattern has been transferred. and 5 to 95 wt% unsaturated group-containing vinyl monomer, TG50 less than ° C and the unsaturated group-containing Bulle monomer 50 weight ^_0/0 or less, chlorinated polypropylene榭脂1-50 ^_0/0 and power also made graft An intermediate coating film containing the polymer as a binder resin is formed. Further, a protective coating film containing an acrylic polyol resin having an OH value of 10 to 200 mg-KOHZg and a polyester polyol resin having a Z or OH value of 10 to 400 mg-KOH / g is formed. Thus, in the said technique, it is necessary to form a protective coating film through an intermediate coating film.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-232998 (Claims 1 to 7, Examples)

Disclosure of the invention

Problems to be solved by the invention

[0006] The problem to be solved by the present invention is to solve the above-mentioned problems, and to provide a coating composition that can give a sense of transparency and a feeling of richness in order to impart the original design properties. It is to provide an article and an article using the article to protect a printed film.

Means for solving the problem

[0007] As a result of intensive studies, the present inventor has found that chlorinated polypropylene-based resin and methacrylic acid A protective coating film obtained by curing a hydroxyl group-containing resin composition obtained by graft polymerization of hexyl, t-butyl methacrylate, and acetyl polyol component consisting of hydroxyethyl methacrylate with a polyisocyanate curing agent. By using it, it was found that a protective coating film having excellent adhesion to both the polypropylene resin molded product and the patterned layer was obtained, and the present invention was completed.

That is, the first aspect of the present invention is water-soluble! / The pattern layer (4) printed on the swellable film substrate (support film) and applied by coating is hydraulically transferred onto the polypropylene resin molded product (3). A protective coating composition that produces a protective coating film (5) having adhesion to both the polypropylene-based resin molded product (3) and the patterned layer (4) against the transferred molded product (2). A polyol component (B) containing at least one selected from the group consisting of a resin component (A) containing at least a modified polyolefin resin (a), an acrylic resin polyol, a polyester polyol, a polycarbonate polyol, and a polyurethane polyol power (B) ) And a hydroxyl group-containing resin composition (P) obtained by the Daraf polymerization and a hydraulic transfer pattern layer protective coating composition comprising a polyisocyanate curing agent (Q).

According to a second aspect of the present invention, in the protective coating composition according to the first aspect of the present invention, a modified polyolefin-based resin (a) power chlorinated polypropylene, acrylic-modified chlorinated polypropylene resin, anhydrous Provided are protective coating compositions that are maleic acid-modified polypropylene, non-chlorinated maleic acid-modified polyolefin resin, and mixtures thereof.

According to a third aspect of the present invention, there is provided a protective coating composition according to the first aspect of the present invention, wherein the composition of the resin composition (P) is 1% to 20% by weight of a resin component (A) and polyol in terms of solid content. Component (B) 99-80% by weight (the sum of both is 100% by weight) is provided.

According to a fourth aspect of the present invention, there is provided the protective coating composition according to the first protective coating composition of the present invention, wherein the polyol component (B) has a glass transition temperature of 50 ° C or higher. According to a fifth aspect of the present invention, in the protective coating composition of the first aspect of the present invention, the polyol component (B) force cyclohexyl (meth) acrylate (b) 5 to 60% by weight, ) acrylic acid t-butyl (c) 5 to 60 weight ^_0/0, styrene (f) 5 to 60 weight ^_0/0, (meth) hydroxy acrylate Shiarukiru (2 to 4 carbon atoms) (d) 3 to 20 wt% And other polymerizations customized as needed A protective coating composition which is an acrylic polyol having a strength of 82% to 0% by weight of the monomer (e) (the total of these components is 100% by weight) is provided.

According to a sixth aspect of the present invention, there is provided the protective coating composition according to the first aspect of the present invention, wherein the hydroxyl value of the resin composition (P) is 10 to: LOOmg-KOHZg To do.

In a ^seventh aspect of the present invention, a patterned layer (4) that is printed on a film base (support film) that is water soluble! The present invention has adhesion to both the polypropylene-based resin molded product (3) and the patterned layer (4) with respect to the transfer molded product (2) obtained by hydraulic transfer onto the product (3). A method for producing a decorative molded article (1) is provided in which the protective coating composition according to any one of the first to sixth aspects is applied and heat-cured.

According to an ^eighth aspect of the present invention, a patterned layer (4) which is printed on a film base (support film) which is water-soluble / tanned and swellable is applied to a polypropylene-based resin molding. Adherence to both the polypropylene resin molded product (3) and the patterned layer (4) on the molded product (3) and the transfer molded product (2) obtained by hydraulic transfer. A decorative molded product (1) comprising a protective coating film formed by applying the protective coating composition according to any one of the first to sixth aspects of the present invention and heat-curing the coating composition is provided.

The invention's effect

[0009] According to the present invention, the transfer molded product obtained by hydraulic transfer has an adhesive property with a polypropylene-based resin molded product that is difficult to adhere, and further has an adhesive property with the pattern layer. It has excellent coating properties such as water resistance, alkali resistance, oil resistance, weather resistance, impact resistance, hardness, and excellent appearance quality such as sharpness, smoothness, and texture. A coating film is obtained.

Further, the protective coating composition is grafted with the resin component (A) containing the modified polyolefin resin (a), which is hardly compatible, and the polyol component (B). As a result, it has excellent storage stability and low viscosity. As a result, it provides excellent design and high appearance quality.

Brief Description of Drawings

FIG. 1 is a configuration diagram of a transfer molded product according to an example. FIG. 2 is a configuration diagram of a decorative molded product according to an example.

Explanation of symbols

[0011] 1 Decorative molded product

2 Transfer molded products

3 Polypropylene resin molded products

4 Pattern layer

5 Protective coating

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] An embodiment of the present invention will be described with reference to Figs.

The protective coating composition of the present invention comprises the polypropylene-based resin molded product 3 and the pattern on the polypropylene-based resin molded product 3 with respect to the transfer molded product 2 obtained by hydraulic transfer of the pattern layer 4. It is a coating composition that produces a protective coating film 5 having excellent adhesion to both the layer 4.

[0013] (I) Polypropylene-based resin molded product

The polypropylene-based resin used in the polypropylene-based resin molded product 3 according to the present invention is not particularly limited as long as it is used in a molded product. For example, polypropylene homopolymer, ethylene, etc. It may be a copolymer of olefin and a ternary or more copolymer obtained by copolymerizing other components such as a linear or cyclic gen component, or those having a functional group added thereto. These may be single or a mixture. As long as these polypropylene-based resins can be used in the present invention, there are no limitations on the type of polymerization catalyst and the molecular weight of the polymer.

Examples of the copolymer include a block copolymer, a random copolymer, a block random copolymer, and the like whose molecular structure is not particularly limited.

Examples of the functional group imparted to the polypropylene-based resin include a carboxyl group, a hydroxyl group, an amide group, an amino group, and the like. These are monomers that are copolymerized at the polymerization stage of the polypropylene-based resin. Even if it is given, it may be given by post-treatment such as chemical treatment, flame treatment, active energy ray treatment after forming into a strand, pellet or molded product. Copolymerization monomers for imparting functional groups include maleic anhydride, maleic acid, fumaric acid , (Meth) acrylic acid, hydroxyethyl (meth) acrylate, butyl acetate, (meth) acrylamide, aminostyrene and the like.

[0014] (Π) Transfer film

The transfer film according to the present invention is water-insoluble or water-swellable on a support film having a thickness of about 5 to 300 m (sometimes referred to as a film substrate or a pattern layer support). The predetermined pattern layer 4 is formed by printing, painting or the like so that the predetermined pattern layer 4 becomes 0.1 to LOO m, usually 1 to 10 m.

[0015] (II— 1) Pattern layer

The material of the pattern layer 4 according to the present invention is hydrophobic and includes the following:

(1) A layer composed of a hydrophobic ink or paint film that can be dissolved in an organic solvent, or (2) a base protective layer composed of an active energy ray-curable resin or a thermosetting resin. There is something that was provided.

The film thickness of the pattern layer 4 is not particularly limited, but is 0.1 to 15 μm, preferably 1 to 10 μm when only the ink or paint film layer is covered. When a coating layer of ink or paint is provided on the undercoat protective layer, it is 1 to 200 m, preferably 10 to: LOO / zm. In any of the above cases, if the film thickness is too thin than the above range, If the required designability and undercoat protection are insufficient and the film thickness is too thick, it becomes difficult to uniformly activate the pattern layer during hydraulic transfer. The activation of the pattern layer can be achieved by applying or spraying an organic solvent to the pattern layer without completely dissolving the resin constituting the decorative layer and, if necessary, the pattern layer consisting of a hardened resin layer. The pattern layer is solubilized to facilitate peeling of the hydrophobic pattern layer such as a hydrophilic support film (pattern layer support or film substrate) during hydraulic transfer, and to make the pattern layer flexible. By imparting, it has the function of improving the followability and adhesion of the patterned layer to the three-dimensional curved surface of the transferred material.

The above ink or paint needs to be activated by an organic solvent, but it is important to have the property of maintaining flexibility to the extent that the pattern does not flow. Gravure printing ink, ink-jet printing ink, epoxy 'urethane resin-based paint , Addition polymer paint, condensation polymer paint Etc.

The varnish resins used in the above inks and paints are acrylic resin, polyurethane resin, polyamide resin, urea resin, epoxy resin, polyester resin, bur resin (vinyl chloride, vinyl acetate copolymer resin), vinyl resin. -Redenic resin (bilidenic lide, vinylidene fluorinate), Ethylene butyl acetate resin, Polyolefin resin, Chlorinated olefin resin, Ethylene-acrylic resin, Petroleum resin, Cellulose derivative resin And the like. Of these, alkyd resin, acrylic resin, polyurethane resin, cellulose-derived resin resin, and ethylene butyl acetate resin are preferable.

Examples of the colorant used in the ink or paint include dyes and pigments, and both inorganic dyes and pigments can be used. Furthermore, it is also possible to use metallic glossy inks containing as a pigment metal strips obtained from metal cutting particle pastes or evaporated metal films.

For the pattern layer, an antifoaming agent, an anti-settling agent, a dye dispersing agent, a fluidity modifier, an antiblocking agent, an antistatic agent, an antioxidant, a light stabilizer, and an ultraviolet absorber as necessary. In addition, various additives for the purpose of improving the internal curing agent and scratch resistance can be added.

[0016] (II-2) Support film (pattern layer support or film substrate)

The support film used for the transfer film is not particularly limited and may be water-soluble or water-swellable. Examples of the material include polybutyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, polyacrylamide, acetyl butyl cellulose, gelatin, sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose, and the like. Further, these components may be used as the main component, and other monomers such as (meth) acrylamide may be copolymerized, or other resins such as polyurethane resin may be combined.

[III] (III) Protective coating composition

The protective coating composition of the present invention comprises a hydroxyl group-containing resin composition (P) and a polyisocyanate curing agent (Q).

[III] (III-1) Hydroxyl-containing resin composition (P)

The hydroxyl group-containing resin composition (P) contains at least the modified polyolefin resin (a). It is obtained by graft polymerization of the resin component (A) and the polyol component (B).

Oil component (A)

The resin component (A) contains at least a modified polyolefin resin (a), and may contain other polyolefin resin (a,) if necessary.

Examples of the modified polyolefin resin (a) include chlorinated polypropylene resin, acrylic modified chlorinated polypropylene resin, maleic anhydride modified polypropylene resin, non-chlorinated maleic acid modified polyolefin resin, and the like. May be used as a mixture of two or more.

Specific examples of the chlorinated polypropylene resin include trade names such as “Sparklon 892L”, “Supercron 814H” and “Supercron 822” manufactured by Nippon Paper Industries Co., Ltd. Specific examples of the acrylic-modified chlorinated polypropylene resin include trade name Supercron 240H and Supercron 223M manufactured by Nippon Paper Industries Co., Ltd.

Specific examples of maleic anhydride-modified polypropylene resin include trade name Superclon 851L and Superclone 930 manufactured by Nippon Paper Industries Co., Ltd.

Specific examples of the non-chlorinated maleic acid-modified polyolefin resin include trade names “Auroren 100” and “Aurolen 200” manufactured by Nippon Paper Chemical Co., Ltd.榭脂composition (P) on a solid basis, modified polypropylene榭脂(a) l~20 weight ^_0/0, preferably from 3 to 18 wt%. If the amount is less than the above range, the adhesion to the polypropylene-based resin product is reduced and peeling occurs. If the amount is more than the above range, the gloss value is greatly reduced and the oil resistance cannot be satisfied. If it is increased, the sharpness is lost and the design properties are completely lost, and the coating film is significantly deteriorated due to oil resistance.

Other polyolefin resins (a ') include low-density, ultra-low-density, high-density, etc. various types of polyethylene, isotactic or syndiotactic polypropylene, propylene / ethylene block or random copolymer, polybutene 1-1, Examples thereof include poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, and cycloolefins.

Other polyolefin resin (a,) is 100 parts by weight of modified polyolefin resin (a). You can add 0-50 parts by weight!

Therefore, the resin component (A) is contained in the protective coating composition in an amount of 1 to 20% by weight, preferably 3 to 18% by weight.

[0020] Polyol component (B)

The polyol component (B) preferably has a glass transition temperature of 50 ° C. or higher. This condition is very close to the adhesion to the polypropylene resin molded product 3 (substrate) and the pattern layer 4. is important. Polypropylene-based resin is a hard-to-adhere material, and in order to adhere it, it is necessary to have a coating film strength as well as a paint system containing polypropylene-based resin. In the newly developed product, it is not sufficient to adhere to the polypropylene resin-molded product 3 (substrate with the polypropylene-containing resin), and it is necessary to supplement it with a polyol component. In addition, since the transferred pattern layer 4 is not completely adhered to the polypropylene resin molded article 3, it is necessary to compensate for this, and the strength and hardness of the coating film are factors that ensure adhesion. It has become.

When the glass transition temperature is described in detail, the coating strength is low at 45 ° C or lower, and the initial adhesiveness peels off, and when it is 45 ° C or higher and lower than 50 ° C, the moisture resistance and heat resistance Secondary adhesion such as adhesion may cause chipping and peeling. And in automobile interior parts, especially in the vicinity of the front, it is under severe conditions against heat and light. Therefore, it is preferable that the glass transition point is 50 ° C. or more as a condition that can withstand them.

In terms of adhesion to polypropylene-based molded resin products 3, excessive shrinkage due to the crosslinking reaction of the coating leads to reduced adhesion, so the glass transition point is preferably 50 ° C or higher, more preferably 60 ° C or higher.

[0021] Examples of the polyol component (B) include those containing at least one selected from the group forces such as acrylic polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, etc., in terms of cost, high appearance, and weather resistance. Acrylic polyol is preferable in consideration of required properties such as heat resistance, chemical resistance and heat resistance.

Acrylic polyols are acetyl polyols containing cycloalkyl (meth) acrylate (b), tert-alkyl (meth) acrylate (c), styrene (f), and hydroxyalkyl (meth) acrylate (d). You can include it. Acrylic polyol is composed of cycloalkyl (meth) acrylate (5 to 8 carbon atoms) (b) 5 to 60 wt%, preferably 10 to 50 wt%; t-alkyl (meth) acrylate (4 to 8 carbon atoms) ) (c) 5 to 60 weight ^_0/0, preferably from 10 to 50 weight ^_0/0; styrene (f) 5 to 60 weight ^_0/0, preferably from 10 to 50 wt%; and (meth) acrylic acid hydroxyalkyl (2 to 4 carbon atoms) (d) 3 to 20% by weight, preferably 5 to 15% by weight; and other polymerizable monomers that can be prepared as required (e) 8 2% by weight or less, preferably Consists of 70% by weight or less, more preferably 50% by weight or less (the total of these components is 100% by weight).

Cycloalkyl (meth) acrylate (b)

Examples of the cycloalkyl (meth) acrylate (b) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, and the like, and preferably cyclo (meth) acrylate. Hexyl.

Cyclohexyl (meth) acrylate is very excellent in compatibility with modified polyolefin resin (a) and greatly contributes to stability over time. Regarding the above compatibility, its compatibility with extremely low polarity to high polarity acrylic resin and urethane resin is accompanied by extremely poor layer separation, gelation, and generation of aggregates. Even if it can be mixed temporarily, it may be difficult to obtain uniform atomization by spray coating. In addition, there are cases in which the poorly soluble power is accompanied by the generation of bumps on the surface of the coating film. The compatibility is very remarkable in terms of storage stability, paintability, and the formation of coatings, and even with respect to coating properties, various performances on an industrial level cannot be achieved without a uniform coating. Nah ... Cyclohexyl methacrylate not only ensures compatibility and stability, but also excels in the transparency of the protective coating, has a high refractive index power, has a sense of depth, provides smoothness, and is required. This greatly contributes to the appearance quality. Furthermore, by greatly reducing the polarity of the rosin-based resin, it contributes to the adhesion to plastic molded products that have poor adhesion and low-polarity polypropylene-based material strength.

In addition, chemical resistance such as water resistance and alkali resistance is also excellent for weather resistance and chemical products containing alcohol.

The composition ratio of the cycloalkyl (b) (meth) acrylate in the polyol component (B) is 5 to 60% by weight, preferably 10 to 50% by weight. And 5 If it is less than%, the transparency is lost and design properties cannot be imparted. On the other hand, if it is more than the above range, the coating film deterioration due to oil resistance is remarkable, which is not preferable.

[0023] t-alkyl (meth) acrylate (c)

Examples of the t-alkyl (meth) acrylate (c) include tert-butyl (meth) acrylate, tert-octyl (meth) acrylate, and preferably tert-butyl (meth) acrylate. .

Like cyclohexyl methacrylate, tert-butyl methacrylate is extremely excellent in compatibility with polypropylene-based rosin, and greatly contributes to stability over time and required appearance quality.

In addition, chemical resistance such as water resistance and alkali resistance is also excellent for weather resistance and chemical products containing alcohol. In addition, tert-butyl methacrylate has the effect of lowering the viscosity of rosin-based resins, mitigating the increase in viscosity caused by graft bonding with polyolefin-based reinforced resin, and as a result, good workability and paintability during painting To improve the wettability, leveling, and flow during application.

The composition ratio of the t-alkyl (c) (meth) acrylate in the polyol component (B) is 5 to 60% by weight, preferably 10 to 50% by weight. If it is less than 10% by weight, the transparency is lowered. If it is less than 5%, transparency is lost, which is not preferable. On the other hand, if it is more than the above range, the coating film deteriorates due to oil resistance, which is not preferable.

[0024] Styrene (f)

Styrene has a high refractive index. The high refractive index of styrene is very effective when transparency and sharpness are required as in the present invention, and greatly contributes to the appearance quality. Styrene is not extremely low in SP (solubility parameter) value, but the skeletal element due to the benzene ring partially contributes to compatibility with polypropylene resin. Styrene is excellent in heat resistance, water resistance and alkali resistance due to the benzene ring in the skeleton. Furthermore, since styrene is an inexpensive raw material, it is useful in paints containing expensive polyolefin resin. In order to make the transfer molded product high appearance specifications, it is preferable to use a low molecular weight resin for the protective coating 5. Polymerization starts because styrene has a low molecular weight function in the polymerization system. In this respect can reduce the agent It is also useful in terms of cost.

The composition of the styrene polyol in component (B) (f) 5 to 60 weight ^_0/0, preferably from 10 to 5 0 wt%, glossiness is required to be 10 wt% or less, DOI It is preferable because the design such as property is deteriorated (the appearance is deteriorated).

[0025] Hydroxyalkyl (meth) acrylate (d)

Examples of the hydroxyalkyl (meth) acrylate (d) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include 2-hydroxybutyl and the like, and preferably 2-hydroxyethyl (meth) acrylate.

The composition ratio of hydroxyalkyl (meth) acrylate (d) in the polyol component (B) is 3 to 20% by weight, preferably 5 to 15% by weight. If it is less than the above range, the chemical resistance is poor. However, the adhesiveness decreases due to curing shrinkage of the coating film.

[0026] Other polymerizable monomer (e)

Examples of the other polymerizable monomer (e) include styrene, α-methylstyrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, η-butyl (meth) acrylate, (Meth) acrylic acid iso-butyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid stearyl, (meth) acrylic acid benzyl, (meth) acrylic acid isobol -Meth, isopentayl (meth) acrylate, and phenoxychetyl (meth) acrylate.

The composition ratio of the other polymerizable monomer (e) in the polyol component (B) is 82% by weight or less, preferably 70% by weight or less.

[0027] Method for producing hydroxyl-containing resin composition (P)

The hydroxyl group-containing resin composition (P) is obtained by graft polymerization of at least the modified polyolefin resin (a) and the polyol component (B) in the resin component (A).

When the graft ratio of the polyol component (B) to the modified polyolefin resin (a) is too small, the storage stability is adversely affected.

As the grafting method, a force lpoxyl group derived from maleic anhydride in a modified polyolefin-based resin is partially reacted with a hydroxyl group-containing bull monomer, or It is obtained by partially reacting a hydroxyl group such as krill-modified polypropylene rosin with an unsaturated group-containing vinyl monomer.

Specifically, when the resin component (A) is dissolved in a solvent under heating, a monomer constituting the polyol component (B), for example, cycloalkyl (meth) acrylate (b), (meth) When t-alkyl talylate (c), styrene (f), hydroxyalkyl (meth) acrylate (d) and other polymerizable monomer (e) added as required are added and stirred uniformly. In addition, a radical polymerization initiator is added and reacted.

Alternatively, graft by chlorine atom extraction reaction with a polymerization initiator such as peroxide.

The thus obtained hydroxyl-containing resin composition (P) has a hydroxyl value of 10 to: LOOmg-KOH / g, preferably 20 to 80 mg-KOHZg. If the hydroxyl value is less than the above range, the coating film performance such as chemical resistance, weather resistance, heat resistance and the like cannot be satisfied. The secondary adhesion, which is moisture-resistant adhesion and water-resistant adhesion, is remarkably lowered, which is preferable.

(III-2) Polyisocyanate curing agent (Q)

The polyisocyanate curing agent (Q) according to the present invention is used for curing the hydroxyl group-containing resin composition (P).

The polyisocyanate curing agent (Q) is composed of a polyisocyanate compound and an amine curing agent added as necessary.

Examples of polyisocyanate compounds include aromatic compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate. Aliphatic compounds such as cyanate and trimethylhexamethylene diisocyanate, and cycloaliphatic compounds such as isophorone diisocyanate and norbornane diisocyanate. In addition, in view of chemical resistance and high appearance, those modified products in which aliphatic compounds are preferred are also included.

Examples of aliphatic isocyanate compounds include Asahi Kasei Kogyo Co., Ltd. trade name Duranate 24A-100, Deyuranate TPA-100, Deyuranate E402-90T, Sumika Bay Urethane trade name Sumidur N-3300, Sumidur N—3200, Smithy N-75, Nippon Polyurethane Industry Co., Ltd., trade name Coronate HX, Coronate EH, Mitsui Takeda Chemical Co., Ltd. trade name Takenate D-165N.

The ratio of the NCO group of the polyisocyanate-based curing agent (Q) to the hydroxyl group of the hydroxyl group-containing resin composition (P) is such that the NCOZOH ratio (equivalent ratio) is 0.5 to 2.0, preferably Rub to 8 to 1.5. If it is less than 8, the chemical resistance and heat resistance are remarkably lowered, and if it is 1.5 or more, the adhesive force is lowered due to excessive curing shrinkage of the coating film.

[0029] (IV) Coating film

When analyzing the surface of a conventional transfer molded product with an electron microscope, numerous holes that can be called gaps can be confirmed, and the pattern layer is in complete contact with the polypropylene-based resin molded product.

Therefore, the protective coating composition of the present invention allows the coating composition to permeate and adhere to the polypropylene-based resin molded product 3 not only from the pattern layer 4 itself but also from the numerous holes present on the pattern layer 4. Intended.

[0030] The coating composition in the present invention is to impart further designability to the pattern layer 4 just by protecting the pattern layer 4 applied on the polypropylene-based resin molded product 3 as described above. In order to give the required protective coating transparency, smoothness, fleshiness, etc., the resin component (A) comprising the modified polyolefin resin (a) and the polyol component (B) described above are used. This is a two-component system in which a grafted hydroxyl-containing resin composition (P) is cured and crosslinked with a polyisocyanate curing agent (Q).

[0031] Method for producing decorative molded product

Using the above transfer film, the pattern layer 4 of this transfer film is hydraulically transferred onto the polypropylene-based resin molded product 3 to produce a transfer molded product 2 as shown in FIG. Since the support film is water-soluble when it floats on the water surface in the transfer tank, it gradually dissolves. After transfer, the support film remaining on the pattern layer is removed by washing with water. Thus, as shown in FIG. 2, the protective coating composition is applied so as to cover the polypropylene-based resin molded product 3 and the pattern layer 4 and is heated and cured to form the protective coating film 5.

Painting method

There are spray coating, brush coating, roller coating, date coating, electrodeposition coating, etc. as coating methods for forming the protective coating 5. Painting is preferred.

The viscosity of the mixed solution at the time of painting is 10 to 15 seconds, preferably 11 to 14 seconds in Ford Cup # 4. After mixing with the specified isocyanate, dilute with an appropriate organic solvent. If the time is less than 11 seconds, repellence frequently occurs on the transfer printing film, and the object to be coated is tilted, and when it is applied, there is a frame phenomenon in which the applied solution flows from the center of the object to be coated to the outside. It is not preferable because it occurs. If it is 14 seconds or longer, the spray atomization property is deteriorated, the dullness to the object to be coated is insufficient, and the smoothness is lacking.

When describing the film thickness of the protective coating film at the time of painting, it is 10 to 50 m, preferably 20 to 40 m, and if it is 15 to 20 / ζ πι, the feeling of holding is slightly lowered, and if it is less than 15 m A feeling of flesh is not expressed and design properties cannot be given, which is not preferable. If it is 40 m or more, problems such as cracks and sagging occur, which is not preferable.

After painting, leave at room temperature for 5-10 minutes and force dry. The drying conditions are 60 to 100 ° C. and 10 to: LOO minutes, preferably 65 to 90 ° C. and 20 to 60 minutes, and the drying temperature is less than 65 ° C. and the crosslinking density is 20 to 60 minutes. The adhesion strength, chemical resistance, and heat resistance are also reduced, and the drying time must be extended. Further, if the temperature is 90 ° C. or higher and 30 to 60 minutes, curing shrinkage accompanying an increase in reaction rate is caused, and adhesion is lowered, which is not preferable.

The decorative molded product 1 is obtained as described above. This decorative molded product 1 is a transfer molded product obtained by hydraulic transfer of a patterned layer 4 printed or coated on a water-soluble or swellable support film onto a polypropylene-based resin molded product 3. 2 and a protective coating film 5 formed by applying and heat-curing the protective coating composition so as to cover at least the pattern layer 4 of the transfer molded product 2. The protective coating 5 is preferably provided so as to cover both the pattern layer 4 and the polypropylene-based resin molded product 3.

[0032] The coating composition of the present invention is mainly intended to provide transparency and fleshiness, and to provide a high appearance. However, the coating composition can be colored such as color clear or treated with an extender pigment. However, excessive addition of extender pigments causes a significant decrease in gloss, so the amount of addition is limited.

Example

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. is not.

[0034] (Production of hydroxyl-containing resin composition (P), Examples 1-2, Reference Examples 1-8)

A 1-liter four-necked flask equipped with a stirrer, cooler, thermometer, and monomer dropping device is charged with the composition shown in Table 1 and the component (A) is added to the internal temperature of 85 ° C while stirring. The sample was warmed up and held at 85 ° C for 20 minutes. Next, component (B) was added dropwise over 2 hours. After completion of the dropwise addition, component (C) was added and polymerized at 85 ° C. for 2 hours to obtain a solution of the hydroxyl group-containing resin composition (P). This solution was further diluted with toluene. In Table 1, the amount of each component used is expressed in parts by weight.

[0035] Table 1 shows Sumidur N-3300 as a polyisocyanate-based hardener (Q) in a solution whose viscosity was adjusted by diluting the obtained hydroxyl-containing resin composition (P) with toluene. I got a quantity.

[0036] Manufacture of transfer molded product 2

A patterned layer 4 was applied to the following polypropylene resin molded product 3 using the following transfer film.

Polypropylene-based resin molding 3 was used by molding surface-treated polypropylene PP—N—AN made by Shin-Kobe Electric Co., Ltd. into a test piece of 6cm (W) X 15cm (L) X 3mm (T). .

As a transfer film, Dainippon Printing Co., Ltd. hydraulic transfer printing sheet (curl fit, thickness 5 to: LO / z m, varnish resin is alkyd resin) was used.

[0037] (Examples 1-2 and Reference Examples 1-8)

Using the coating composition obtained above on the transfer molded product 2 obtained above, a protective coating film 5 is applied by spray coating so that the thickness after coating is 20 to 40 111. Formed

[0038] Table 1 shows the results regarding the appearance, initial adhesion, and secondary adhesion of the protective coating film of the decorative molded article 1 obtained by Examples 1-2 and Reference Examples 1-8.

(1) Appearance: Judging from the 60 ° gloss obtained by measuring with a gloss meter, ○ is 90 or more, △ is 80 to 90, and X is less than 80.

(2) Adhesion: The following adhesion test (gap lmm, number of meshes 100) was conducted according to JIS Κ5400 Γ8. Initial adhesion: A protective coating is formed, and the adhesion after 72 hours at room temperature is measured.

Secondary adhesion:

(2-1) Heat-resistant adhesion: A protective coating is formed, and after standing for 72 hours at room temperature, the adhesion after a 300-hour heat test at 80 ° C is measured.

(2-2) Moisture-resistant adhesion: After forming a protective coating and leaving it at room temperature for 72 hours, measure the adhesion after a 500-hour humidity resistance test in an atmosphere of 50 ° C and humidity 95% RH.

Both initial adhesion and secondary adhesion are based on the following criteria.

◯ indicates that there is no trace of peeling, △ indicates peeling is 1 or more and less than 10 Z100, and X indicates peeling is 10 or more and Z100.

(3) Oil resistance: A protective coating film was formed and allowed to stand at room temperature for 72 hours, and then immersed in heptane, which is a low polarity solvent, at room temperature for 1 hour.

◯ indicates no deterioration of the coating film, Δ indicates slight deterioration, and X indicates that the coating film is clearly deteriorated.

(4) Storage stability: A toluene-diluted solution of the above hydroxyl group-containing resin composition (P) is allowed to stand at 0 ° C, 20 ° C, 40 ° C, 60 ° C to separate layers and gelate over time. The presence or absence of aggregates was judged visually.

[table 1]

Actual] 6 examples Reference examples

Protective paint composition 1 2 1 2 3 4 5 6 7 8 Resin composition (P)

(A) Composition of ingredients

Chlorinated PP (* 125 375 75 450 125 125 125 125 125 125 Toluene 380 180 420 ― 380 380 380 380 380 380

(B) Composition of ingredients

n-BA (*) 15 ― 33 8 10 10 One 50 234 282 i-BMA 3) 23 38 67 15 13 160 18 ― One ―

St (* 60 50 49 50 55 148 193-54 48 tert-BMA (*) 143 128 97 103 133 100-150 51 44

CHMA 6) 190 170 194 190 170 13 220 220 81 46

HE A 44 39 45 44 94 44 44 55 55 55

OHV (mg / KOH) 40 40 40 46 85 40 40 50 50 50 Power 'lass transition temperature (° c) 86 87 77 86 84 77 88 80 49 42

(C) Component composition

Polymerization initiator 4 4 4 4 4 4 4 4 4 4 Diluent (toluene) 20 20 20 20 20 20 20 20 20 20 Non-volatile components (%) 50 50 50 50 50 50 50 50 50 50 Storage stability ○ ○ OXOO ○ △ 〇 Δ Hardener (Q)

Sumidur N3300 78 70 63 61 165 78 78 98 98 98 Evaluation of protective coatings

Appearance ○ O ○ X ○ XXOX ○ Initial adhesion ○ ○ X ○ Δ ○ ○ O △ X Moisture-proof adhesion ○ ○ X ○ XO ○ ○ XX Heat-resistant adhesion 0 ○ X ○ X ○ O ○ XX Oil resistance ○ ○ OX ○ ○ OXO ○

(¾U) Nippon Paper Industries Co., Ltd., chlorinated polypropylene resin (trade name Supercron 892L, chlorination rate 20%, 20% toluene solution)

(*?) N-butyl acrylate

3) Iso-butyl methacrylate

Replacement paper (fine IJ26) (* Styrene

(* 5) tert-butyl methacrylate

(* 6) Cyclohexyl methacrylate

(* 7) 2-hydroxyethyl methacrylate

* 8) Azobisisobuti mouth-tolyl

In Table 1, OHV represents the hydroxyl value.

[0041] From the results in Table 1, Reference Example 1 has a low chlorinated polypropylene resin content of 3% by weight, and thus the adhesion is not sufficient. In Reference Example 2, the appearance is not sufficient because the chlorinated polypropylene resin is too much at 18% by weight. Reference Example 3 has a hydroxyl value of 85 mgZKOH and a high crosslink density, so the adhesion is not sufficient. In Reference Example 4, since CHMA is 2.7% by weight, the appearance due to the decrease in transparency is reduced. In Reference Example 5, since t-BMA is 0.0%, the appearance due to a decrease in transparency is deteriorated. In Reference Example 6, since St is 0.0%, the appearance is deteriorated due to a decrease in transparency. In Reference Example 7, the glass transition temperature is 50 ° C or lower, so the adhesion is not sufficient. In Reference Example 8, since the glass transition temperature is 40 ° C or lower, the adhesion is not sufficient.

Industrial applicability

[0042] With respect to a transfer molded product obtained by hydraulic transfer of a pattern layer to a polypropylene-based resin molded product, adhesion with a polypropylene-based resin molded product that is difficult to adhere is further improved. It has excellent coating performance such as water resistance, alkali resistance, oil resistance, weather resistance, impact resistance, hardness, and appearance quality such as sharpness, smoothness, and texture. Can also provide excellent protective coatings.

Claims

The scope of the claims

[1] For a transfer molded product obtained by water-transferring a pattern layer applied by printing and coating on a water-soluble, swellable film substrate onto a polypropylene resin molded product. A protective coating composition for producing a protective coating having adhesion to both the polypropylene-based resin molded product and the pattern layer,

A resin component (A) containing at least a modified polyolefin resin (a) and

A hydroxyl group-containing resin composition (P) obtained by graft polymerization with a polyol component (B) containing at least one selected from the group strength of acrylic polyol, polyester polyol, polycarbonate polyol, and polyurethane polyol.

And polyisocyanate curing agent (Q)

A coating composition for protecting a hydraulic transfer pattern layer.

[2] Modified polyolefin-based resin (a) force A chlorinated polypropylene, acrylic-modified chlorinated polypropylene resin, maleic anhydride-modified polypropylene, non-chlorinated maleic acid-modified polyolefin resin, and a mixture thereof Item 1. The protective coating composition according to Item 1.

[3] The resin composition (P) is, in terms of solid content, a resin component (A) 1 to 20% by weight and a polyol component (B) 99 to 80% by weight (the total of both is 100% by weight) The protective coating composition according to claim 1, which comprises:

[4] The protective coating composition according to claim 1, wherein the polyol component (B) has a glass transition temperature of 50 ° C or higher.

[5] The polyol component (B), (meth) hexyl acrylate cyclo (b) 5 to 60 wt%, (meth) § acrylic acid t-butyl (c) 5 to 60 weight ^_0/0, styrene (f) 5-60 weight ^_0/0, (meth) acrylic acid ratio mud carboxyalkyl (2-4 carbon atoms) (d) 3 to 20 wt% and optionally Ca卩example is the other polymerizable monomer (e The protective coating composition according to claim 1, which is an acryl polyol comprising 82 to 0% by weight (the total of these components is 100% by weight).

[6] The protective coating composition according to claim 1, wherein the resin composition (P) has a hydroxyl value of 10 to: LOOmg—KOHZg.

[7] Transfer-molded product obtained by hydrostatic transfer of water-soluble! (2) A method for producing a decorative molded product, in which the protective coating composition according to any one of claims 1 to 6 is coated and heat-cured, having adhesion to both a polypropylene-based resin molded product and the pattern layer. .

A transfer molded product obtained by water-transferring a pattern layer applied by printing and coating on a water-soluble swellable film substrate onto a polypropylene-based resin molded product, and the transfer composition A protective product obtained by applying a protective coating composition according to any one of claims 1 to 6 having adhesion to both the polypropylene-based resin molded product and the patterned layer on a shaped product, followed by heat curing. A decorative molded product consisting of a coating film.